CN1018830B - Process for decreasing ketene tripolymer in diketen products - Google Patents
Process for decreasing ketene tripolymer in diketen productsInfo
- Publication number
- CN1018830B CN1018830B CN88102282.9A CN88102282A CN1018830B CN 1018830 B CN1018830 B CN 1018830B CN 88102282 A CN88102282 A CN 88102282A CN 1018830 B CN1018830 B CN 1018830B
- Authority
- CN
- China
- Prior art keywords
- diketene
- ketene
- raw product
- organic compound
- trimer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/87—Preparation of ketenes or dimeric ketenes
- C07C45/90—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
Abstract
Process for the reduction of the ketene trimer portion in raw diketene by mixing of the diketene with water, an alcohol, a phenol or a carboxylic acid, and heating the mixture to 50 DEG to 130 DEG C..
Description
The present invention relates to a kind of processing method that is used for reducing diketene ketene trimer (Ketentrimer) content.
Just as known, in the dimerisation process of ketene, except that diketene as the primary product, also generate polymerization resin and ketene trimer, this ketene trimer is used as 3-acetate basic ring fourth-2 alkene-1-ketone (3-Acetoxycyclobut-2-en-l-on) and is differentiated that its content in diketene is about 5%.
People know that also this ketene trimer when heating surpasses 50 ℃ the 975th page of beginning of violent thermopositive reaction (Helv.Chim.Acfa 60(1977) the 100th phase can take place).Produce the performance of uncontrollable thermopositive reaction during this heating of ketene trimer, bring suitable danger for the production and the distillation of diketene.
Task of the present invention is, ketene trimer is removed from the raw product diketene or reduced its content in simple mode.This purpose can be accomplished by employing method as described below:
Reduce the method for ketene trimer component content in the diketene raw product, it is characterized in that: with diketene mix with contained ketene trimer respective amount wherein, general expression formula is
Compound, R=H wherein, or expression includes the alkyl or phenyl of 1 to 18 carbon atom, X=oxygen or sulphur or XH=COOH-group, and n=1 or 2; Then, be heated to 50-130 ℃ of temperature and distill out diketene.
Can adopt water, unit alcohol or polyvalent alcohol, monobasic or polyphenol, thio-alcohol, polythiol class or the carboxylic acid of 1 to 18 carbon atom are arranged as compound R (XH) n.These compounds can as:
Alcohols: methyl alcohol, ethanol, propyl alcohol, enanthol, stearyl alcohol, glycol ether (Diethyl-englykol)
Phenols: phenol, Resorcinol
Thio-alcohol: butanethiol, Stearyl mercaptan
The multi-thiol class: 1,3-butyl two mercaptan (1,3-Butyldithiol)
1, and 10-decyl two mercaptan (1,10-Decandithiol)
Acids: formic acid, acetic acid, oxalic acid, propanedioic acid, succsinic acid
Preferentially select the alcohols or the phenols that contain 1 to 6 carbon atom in the molecule for use.
When the time was 0.25 to 5 hour, suitably keeping temperature was 50 to 130 ℃, and diketene just can distill safely then.
When adopting molecular formula is R(XH) during the compound treatment diketene raw product of n, produce heat stable butylene carboxylic acid derivative (Buten-carbonsaeurederivate), its expression formula
This inventive method can be carried out with batch process (Batchverfanren) or continuous process in the reactor of stirring is arranged.
Embodiment 1:
Get one kilogram and contain the trimeric diketene raw product of 4.2% ketene, add in the constant temperature stirring tank be equipped with equivalent methyl alcohol 65 minutes internal heating to 60 ℃-63 ℃.Through this processing, ketene trimer content wherein drops to the limit value of regulation, and this moment, this raw material diketene that does not in fact contain ketene trimer just can distill under the situation that degree of safety improves greatly.
Embodiment 2:
Get 0.1 kilogram of diketene raw product, wherein contain 4.3% ketene trimer, put into the constant temperature stirred vessel of the glycol ether (Diethylenglykol) that is equipped with half mole that is equivalent to ketene trimer, at 60 minutes internal heating to 60-65 ℃, through this processing, ketene trimer content reduces to 3.1%.
Embodiment 3:
Get 0.1 kilogram of diketene raw product and 9.22 gram Stearyl alcohols mixing, be heated to 60-65 ℃ within a short period of time, and this temperature was kept 70 minutes.At this moment the content of ketene trimer counts 1.8% in the cooled sample, and this value is equivalent to the trimeric content of ketene and has descended 2.5%.
Embodiment 4:
Carrying out two tests with the same mode of embodiment 1-3, with 0.1 kilogram of diketene raw product respectively with 3.21 gram phenol, 1.88 gram Resorcinol hybrid reactions.These at room temperature the refrigerative sample shown the drop-out value of following ketene trimer:
Handle sample for phenol: handle back ketene trimer content and reduce 0.3%.
Handle sample for Resorcinol: handle back ketene trimer content and reduce 1.8%.
Embodiment 5:
0.1 the mixed solution of kilogram diketene raw product and 9.77 gram 1-Stearyl mercaptans (1-Oc-tadecanthiol) is heated to 60-65 ℃ within a short period of time, and this temperature was kept 0.5 hour.After temperature was elevated to 95-100 ℃, the content of ketene trimer reduced to 3.3% from 4.8% in the reaction mixture.
Embodiment 6:
Get 5 parts of 0.1 kilogram of raw product diketenes, with 2.38 gram acetic acid, 8.74 gram hexadecanoic acids, 1.77 gram propanedioic acid, 2.01 gram succsinic acids and 4.16 gram phenylformic acid, at room temperature mix respectively, mixed solution is heated to temperature of reaction within a short period of time.So just can observe the decline situation of ketene trimer content:
The carboxylic acid reaction temperature (℃) reaction times (h) ketene trimer
Content reduces (%)
Acetic acid 62-63 1.17 2.7
Hexadecanoic acid 62 1.17 2.8
Propanedioic acid 60-65 1.0 4.4
Succsinic acid 62-63 1.17 3.5
Phenylformic acid 62 1.17 2.8
Embodiment 7:
Get 0.1 kilogram of diketene raw product, mix with 0.61 gram water under the room temperature, and be heated to 60-65 ℃ within a short period of time, this reaction mixture temperature is continued 70 minutes.After cooling under 20 ℃ of temperature, the content of ketene trimer has descended 3.1% in the diketene raw product with reaction mixture.
Claims (4)
1, reduces the method for ketene trimer component content in the diketene raw product, it is characterized in that: the diketene raw product is mixed so that wherein the water and the general expression formula of contained ketene trimer respective amount are
Organic compound, R=H wherein, or expression includes the alkyl or phenyl of 1 to 18 carbon atom, X=oxygen or sulphur or XH=COOH-group, and n=1 or 2; Then, be heated to 50～130 ℃ of temperature and distill out diketene.
2, the method described in claim 1, it is further characterized in that the organic compound that is adopted is the fatty alcohol that contains 1 to 18 carbon.
3, the method for claim 1, it is further characterized in that the organic compound that is adopted is phenol or multi-phenol (n=1 or 2).
4, the method for claim 1, it is further characterized in that the organic compound that is adopted is monocarboxylic acid or di-carboxylic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1489/87 | 1987-04-16 | ||
| CH1489/87A CH668971A5 (en) | 1987-04-16 | 1987-04-16 | METHOD FOR REDUCING THE KETETRIMER CONTENT IN DIKETEN. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN88102282A CN88102282A (en) | 1988-11-02 |
| CN1018830B true CN1018830B (en) | 1992-10-28 |
Family
ID=4211662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88102282.9A Expired CN1018830B (en) | 1987-04-16 | 1988-04-15 | Process for decreasing ketene tripolymer in diketen products |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4808735A (en) |
| EP (1) | EP0287894B1 (en) |
| JP (1) | JPS63258866A (en) |
| CN (1) | CN1018830B (en) |
| CA (1) | CA1311208C (en) |
| CH (1) | CH668971A5 (en) |
| DE (1) | DE3876480D1 (en) |
| IN (1) | IN171051B (en) |
| SU (1) | SU1579453A3 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4239117A1 (en) * | 1992-11-20 | 1994-05-26 | Wacker Chemie Gmbh | Process for the isolation of pure diketene with recovery of valuable materials |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2848496A (en) * | 1958-08-19 | Dimerisation of ketenein medium of | ||
| US2802872A (en) * | 1954-04-09 | 1957-08-13 | Hoffmann La Roche | Preparation of diketene |
| US3000906A (en) * | 1960-02-05 | 1961-09-19 | Eastman Kodak Co | Purification of pivalolactone |
| CH421080A (en) * | 1963-11-29 | 1966-09-30 | Lonza Ag | Process for reducing resin formation in the manufacture and storage of diketene |
| JPS61176581A (en) * | 1985-01-31 | 1986-08-08 | Daicel Chem Ind Ltd | Method of purifying diketene |
-
1987
- 1987-04-16 CH CH1489/87A patent/CH668971A5/en not_active IP Right Cessation
-
1988
- 1988-04-05 US US07/177,609 patent/US4808735A/en not_active Expired - Fee Related
- 1988-04-06 EP EP88105486A patent/EP0287894B1/en not_active Expired - Lifetime
- 1988-04-06 DE DE8888105486T patent/DE3876480D1/en not_active Expired - Fee Related
- 1988-04-07 SU SU884355505A patent/SU1579453A3/en active
- 1988-04-11 JP JP63088861A patent/JPS63258866A/en active Pending
- 1988-04-14 CA CA000564129A patent/CA1311208C/en not_active Expired - Fee Related
- 1988-04-15 CN CN88102282.9A patent/CN1018830B/en not_active Expired
- 1988-04-18 IN IN243/MAS/88A patent/IN171051B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| SU1579453A3 (en) | 1990-07-15 |
| CH668971A5 (en) | 1989-02-15 |
| IN171051B (en) | 1992-07-04 |
| EP0287894A3 (en) | 1990-04-25 |
| DE3876480D1 (en) | 1993-01-21 |
| CA1311208C (en) | 1992-12-08 |
| JPS63258866A (en) | 1988-10-26 |
| US4808735A (en) | 1989-02-28 |
| CN88102282A (en) | 1988-11-02 |
| EP0287894A2 (en) | 1988-10-26 |
| EP0287894B1 (en) | 1992-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0148729B1 (en) | Process for the preparation of sterically hindered hydroxyphenylcarboxylic-acid esters | |
| EP0527224B1 (en) | Production of hydroxy fatty acids and estolide intermediates | |
| EP0102920A1 (en) | Process for the preparation of sterically hindered hydroxyphenyl carboxylic-acid esters | |
| DE69206162T2 (en) | Transvinylation process by reactive distillation. | |
| DE3719790A1 (en) | MANUFACTURE OF LONG-CHAIN POLYOLS FROM RENEWABLE RAW MATERIALS | |
| EP0126349A1 (en) | Process for the preparation of 4-pentenoic-acid esters | |
| AU714151B2 (en) | Processes for the preparation of 3-(methylthio)propanal and 2-hydroxy-4-(methylthio)butanenitrile | |
| EP0118639A1 (en) | Synthesis of acrylic or methacrylic acid esters | |
| EP1569890B1 (en) | Method for producing linear or branched fatty acid esters by means of heterogeneously catalysed reactive rectification with an upstream reactor | |
| CN1018830B (en) | Process for decreasing ketene tripolymer in diketen products | |
| DE68904692T2 (en) | METHOD OF PRODUCING CYCLOHEXANOL. | |
| US2493637A (en) | Process for the preparation of aliphatic nitriles | |
| CA1140573A (en) | Process for the preparation of delta keto-acids and derivatives thereof | |
| US6307106B1 (en) | Process for preparing unsaturated ketones | |
| EP0285899B1 (en) | Process for the preparation of maleic-acid dimethyl ester | |
| US4488997A (en) | Method for the preparation of higher antimony tricarboxylates | |
| EP0072401A1 (en) | Method for the preparation of aliphatic nitriles | |
| JP2022546018A (en) | Method for producing α-hydroxy ester by esterification of α-hydroxy acid | |
| DE19815833A1 (en) | Process for the preparation of linalyl acetate | |
| EP0590557B1 (en) | Process for preparing acetoxystyrene | |
| EP0574725B1 (en) | Process for the preparation of vinyl esters of halogenacetic acid | |
| GB1596651A (en) | Process for the recovery of laevulinic acid in the form of its internal ester alphaangelica lactone from mixtures of compounds of similar boiling-point | |
| DE3783431T2 (en) | METHOD OF PRODUCING 2,6-DIACETOXYNAPHTHALEN. | |
| US4171458A (en) | Manufacture of α-naphthol | |
| EP0465723A1 (en) | Process for the preparation of ditertiary butoxy-diacetoxysilane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |